Intramolecular surfaces for vicinal proton–proton coupling constants 3JHH

Equations for the intramolecular surfaces of the 3JHH coupling constants in ethane, ethylene, and acetylene are formulated, and the corresponding coefficients are estimated from calculations at the DFT/B3LYP level. The chosen variables are changes in bond lengths, in the torsion angle φ between the coupled protons Ha and Hb, in bond angles, and in dihedral angles. The 3JHH surface of ethane is formulated as an extended Karplus equation with the coefficients of a truncated Fourier series on the torsion angle φ expanded as second-order Taylor series in the chosen variables taking into account the invariance of 3JHH under reflections and rotations of nuclear coordinates. Partial vibrational contributions from linear and square terms corresponding to changes in the geometry of the Ha − Ca − Cb − Hb fragment are important while those from cross terms are small with a few exceptions. The 3JHH surface of ethane is useful to predict contributions to 3JHH from changes in local geometry of derivatives but vibrational contributions are predicted less satisfactorily. The predicted values at the B3LYP/BS2 level of the 3JHH couplings (vibrational contributions at 300 K) from equilibrium geometries are 9.79 (−0.17) for acetylene, and 17.08 (1.93) and 10.73(0.93) for the trans and cis couplings of ethylene.

History of health, a valuable tool in public health

The aim of this article is to highlight the importance of the history of public health for public health research and practice itself. After summarily reviewing the current great vitality of the history of collective health oriented initiatives, we explain three particular features of the historical vantage point in public health, namely the importance of the context, the relevance of a diachronic attitude and the critical perspective. In order to illustrate those three topics, we bring up examples taken from three centuries of fight against malaria, the so called “re-emerging diseases” and the 1918 influenza epidemic. The historical approach enriches our critical perception of the social effects of initiatives undertaken in the name of public health, shows the shortcomings of public health interventions based on single factors and asks for a wider time scope in the assessment of current problems. The use of a historical perspective to examine the plurality of determinants in any particular health condition will help to solve the longlasting debate on the primacy of individual versus population factors, which has been particularly intense in recent times.

The circumstellar environment and evolutionary status of the supergiant B[e] star Wd1-9

Context. Historically, supergiant (sg)B[e] stars have been difficult to include in theoretical schemes for the evolution of massive OB stars. Aims. The location of Wd1-9 within the coeval starburst cluster Westerlund 1 means that it may be placed into a proper evolutionary context and we therefore aim to utilise a comprehensive multiwavelength dataset to determine its physical properties and consequently its relation to other sgB[e] stars and the global population of massive evolved stars within Wd1. Methods. Multi-epoch R- and I-band VLT/UVES and VLT/FORS2 spectra are used to constrain the properties of the circumstellar gas, while an ISO-SWS spectrum covering 2.45−45μm is used to investigate the distribution, geometry and composition of the dust via a semi-analytic irradiated disk model. Radio emission enables a long term mass-loss history to be determined, while X-ray observations reveal the physical nature of high energy processes within the system. Results. Wd1-9 exhibits the rich optical emission line spectrum that is characteristic of sgB[e] stars. Likewise its mid-IR spectrum resembles those of the LMC sgB[e] stars R66 and 126, revealing the presence of equatorially concentrated silicate dust, with a mass of ~10−4M⊙. Extreme historical and ongoing mass loss (≳ 10−4M⊙yr−1) is inferred from the radio observations. The X-ray properties of Wd1-9 imply the presence of high temperature plasma within the system and are directly comparable to a number of confirmed short-period colliding wind binaries within Wd1. Conclusions. The most complete explanation for the observational properties of Wd1-9 is that it is a massive interacting binary currently undergoing, or recently exited from, rapid Roche-lobe overflow, supporting the hypothesis that binarity mediates the formation of (a subset of) sgB[e] stars. The mass loss rate of Wd1-9 is consistent with such an assertion, while viable progenitor and descendent systems are present within Wd1 and comparable sgB[e] binaries have been identified in the Galaxy. Moreover, the rarity of sgB[e] stars - only two examples are identified from a census of ~ 68 young massive Galactic clusters and associations containing ~ 600 post-Main Sequence stars - is explicable given the rapidity (~ 104yr) expected for this phase of massive binary evolution.